5. A B B A B A B B A A B A B 2 A [A] B [B] 51 v = k[a][b] 51 A B 3 0 273.16 A B A B A B A A [A] 52 v= k[a] 52 A B 55
2 A B A B A A B Ea 1 51 Ea 1 A B A B B A B B A Ea 2 A B Ea 1 ( )k 1 Ea 1 Ea 2 Arrhenius 53 Ea 2 2 53 R T k 1 = χe 1 Ea RT k 2 = χe 2 Ea RT 53 A B A B A 53 52 A B 56
A B G 43 S 54 K 53 54 55 G = Ea 2 Ea 1 = TS Ea Ea RT G RT T S RT k2 K = = χe = χe = χe = χe k 1 2 1 54 S RT R 55 57
1 27 A B 53 G0 1kcal/mol 3:1 3kcal/mol 99.4 55 T 3 3 4 van der Waals 58
51 20 1 0.17 e 0.15 N 3 526000.00 Ne 0.98 3 2 119.31 N 2 2.37 2 4 15.36 2 4.47 S 3846.00 Ar 6.39 2 168.06 N 2 117.11 S 2 112800.00 51 Kr 28.80 Xe 72.97 59
2 3 2 1 3 3 l Br N 3 N 3 2 3 P 4 2 S 2 S 4 2 Na 36 47.5 88 63.5 37 21.5 9.6 7.7 15.8 19.8 K 34 65.2 31.6 112 71.5 52.5 24.9 159 107 Mg 2 54.5 96.5 42.1 26.2 a 2 74.5 143 56.39 0.17 4x10 3 0.17 2x10 2 0.208 Ba 2 35.7 104 9.2 3.89 2x10 3 2x10 2 Al 3 47.3 73 9x10 4 26.7 Fe 2 37.6 53.5 45.6 7x10 6 7x10 5 26.5 Fe 3 91.9 46.6 o 2 34.6 50 3x10 4 4x10 3 4x10 4 26.5 Ni 2 39.6 56.7 48.5 1x10 3 9x10 3 37.8 u 2 41.5 55.9 55.58 3x10 5 3x10 5 20.7 Zn 2 367 81.7 117.5 4x10 4 5x10-5 53.8 60
52 K Na Mg a Ba Fe Al 51 2.59 4.8 8.02 12.9 19.11 28.7 6.9 9.6 12.7 16.4 109 129 174 35.7 36 36.6 37.3 38.4 39.8 27.6 34 40 45.5 51.1 56.7 29.4 37.2 45.8 55.2 65.6 77.3 52.8 54.5 57.5 61 66 73 74.4 91.9 14.3 20.7 28.5 40 55 75.4 3 6 13.6 35.3 154 2.75 3.4 0.17 0.29 0.56 1.16 2.8 6.46 2.8 6.9 16.2 35.8 70.8 122.9 141.8 225.2 331.6 452.6 671.7 3.41 7.17 15.08 31.69 140 9.2 22.6 43.3 78.3 125 185 61
55 S T 53 0 100 2 100 20 Brønsted A A B B 54 1s 1s 2 A A B B 2 Lewis 2 62
A A A B A B 52 51 56 0 56 57 v=-k a [A]k b [ ][A - ] K A = k a = [ ][A - ] k b [A] [A] [ ]=K A [A - ] pk a =-log(k A ) 56 57 58 59 K A 55 57 58 59 pka 54 pka pka 5.20 4.75 0.3 pka B B 56 510 63
54 pka25 pka l l 7.00 S 4 S 4 5.20 N 3 N 3 1.40 S 4 S 4 2 1.92 3 P 4 P 4 2.12 3.75 6 5 6 5 4.19 3 3 4.75 3 3 6.37 S S 7.04 P 4 P 4 2 7.21 N N 9.10 3 B 3 B 3 9.14 6 5 6 5 9.89 3 3 2 10.25 S S 2 11.96 P 4 2 P 4 3 12.67 B 3 B 3 2 12.74 B 3 2 B 3 3 13.80 3 3 15.00 15.70 3 3 3 20.00 N 3 N 36.00 6 6 6 5 43.00 0 510 511 511 57 512 pka 55 pka 64
55 pka25 pka 4 6 N 4 5 N 2.9 3 1.7 NN 3 3 N 3 ( ) 2 ()N 3 5 6 N 4 2 3 ()N 3 5 4 N 4 N 3 2 NN 0.1 3 N 0.63 ( ) 2 ( )N 3 5 5 N 4 3 ( )N 3 5 3 N 4 N 3 ( ) 2 ( )N 3 ( ) 2 ( )N 3 6 5 N 3 3 N ( ) 4 ()N 3 510 511 512 pka 9.25 4.63 pka 2.13 2.3 2.35 4.12 4.31 6 5 N 4.63 N( ) 4 ( )N 3 5 6 N 5 5 N 5.25 3 5 N 2 5 5 N 4 N 4 5.05 3 4 N 2 6.95 5 4 N 4 8.96 N 3 9.25 ( 3 ) 3 N ( 3 ) 3 N 9.81 5 3 N 4 N 3 N( ) 4 ( )N 3 3 N 3 ( 3 ) 2 N 5 3 N 4 N 9.83 N( ) 4 ( )N 10.53 3 N 10.66 ( 3 ) 2 N 10.73 3 4 N 2 3 4 N 2 14.3 v=-k b [ ][B]k a [B ] K B = k a = [ ][B] k b [B ] [ [B ]=K ] B [B] 65
Brønsted A A B B (A) (B) B A 58 512 513 [B ][A - ] K = A [B][A] KB 513 55 pka 7.00 9.25 513 10 16.25 R R N X N X pka R=: X=l: R= 4.75 4.63 6 5 : X= 3 : 10 0.08 pka 15.7 56 pka 1.7 3 pk a :-1.7 514 2 pk a :15.7 66
N 4 pka 515 pka 3 516 2 A A K A B B K B 55 [ ][N 3 ] KN 4 10 = = -9.25 10-15.70 = 10 6.45 [ - ][N 4 ] K [ ][S - 4 ] K S 4 10 = = 5.20 10-15.70 = 10 20.90 [ - ][ S 4 ] K [ ][ S 4 ] K 3 [ 3 ][S - = = = 10-3.50 4 ] K 101.70 S 4 10 5.20 514 515 516 2 3 67
57 3 13 10 27 1 ( ) n ( ) n ( ) n 3 3 3 n=1216 3 3 3 3 3 2 3 2 2 2 3 2 3 3 3 68
2 2 2 2 2 69
2 58 2 16 18 5 17 15 17 70
m n n m n m Na m n n=15or17,m=31or33or35 Brønsted 2 pka pka pka pka<1 pka pka pka 56 56 pka 8 pka 4.9 pka pka p 518 pka 56 Na 3 71
1 p = pka 2 ( log 14) 3.75 Na 8.4 4.76 3 Na 8.9 4.87 3 Na 8.9 4.83 3 ( ) 2 Na 8.9 4.84 3 ( ) 3 Na 8.9 4.86 3 ( ) 4 Na 8.9 4.89 3 ( ) 5 Na 8.9 4.89 3 ( ) 6 Na 8.9 4.95 3 ( ) 7 Na 9.0 4.90 3 ( ) 8 Na 9.0 4.21 6 5 Na 8.6 9.99 6 5 Na 11.5 10.26 3 6 4 Na 11.6 0.70 6 5 S 3 Na 7.0 15.74 Na 13.0 15.54 3 Na 13.0 16.00 3 Na 13.0 14.16 Na 13.6 10.50 3 SNa 11.8 10.66 3 ( ) 3 SNa 11.8 7.80 6 5 SNa 10.4 72
R 1 R S 5 S R S S R 2 3 R 4 2 S R R R P 6 2 7 3 3 3 3 3 3 R N R R N R R N 3 N 2 9 10 2 11 2 12 8 R R R 13 14 15 16 R 17 18 19 R R R N 73
3 59 R 1218 pka0.70-3.00 Ka2.12 594 510 597 12 4 S 3 12 5 12 5 S Al 2 3 S 4 Na 12 5 4 4 S Na 74
5 911 12 1 1 511 n 5914 Ag 2 R Na R 13 Na R R 15 75
1950 PET (B) (A) 76
55 2 512 van t off A B 519 V b T R ΠV = n b RT 519 c b ρ b M b 520 Π = c b RT ρbrt = M b 520 2 512 3.6 77